Use of supported palladium/gold catalysts in the preparation of tertiary butyl alcohol from tertiary butyl hydroperoxide

Abstract: A method for preparing tertiary butyl alcohol wherein a feedstock comprising a solvent solution of tertiary butyl hydroperoxide in tertiary butyl alcohol or a mixture of tertiary butyl alcohol with isobutane is charged to a hydroperoxide decomposition reaction zone containing a catalytically effective amount of a hydroperoxide decomposition catalyst consisting essentially of alumina having gold-promoted palladium deposited thereon and is brought into contact with the catalyst in liquid phase with agitation under hydroperoxide decomposition reaction conditions to convert the tertiary butyl hydroperoxide to decomposition products, principally tertiary butyl alcohol.

Description: This invention relates to the catalytic decomposition of tertiary butyl hydroperoxide (TBHP). More particularly, this invention relates to a method for the preparation of tertiary butyl alcohol (TBA) by the catalytic decomposition of tertiary butyl hydroperoxide. Still more particularly, this invention relates to a method wherein an alumina supported palladium/gold catalyst is used to catalyze the substantially selective decomposition of tertiary butyl hydroperoxide to tertiary butyl alcohol. It is known to react isobutane with oxygen, either thermally or catalytically, to form a peroxidation reaction product wherein the principal peroxide that is formed is tertiary butyl hydroperoxide. It is also known to thermally or catalytically decompose the tertiary butyl hydroperoxide to form tertiary butyl alcohol. In the text entitled "Organic Peroxides" edited by Daniel Swern (Wiley Interscience, a Division of John Wiley & Sons, New York), in Vol. II on page 157 it is stated that the metal-ion-catalyzed decomposition of primary hydroperoxides yields mainly alcohols, aldehydes and carboxylic acids, citing as an example the decomposition of hydroxymethyl hydroperoxide with aqueous ferrous sulfate to provide formaldehyde, formic acid and water. Sanderson et al. disclose the use of a variety of catalysts for the decomposition of tertiary butyl hydroperoxide in a series of U. S. patents, including a catalyst composed of unsupported nickel, copper, chromia and iron (U. S. Patent No. 4,704,482), a catalyst composed of iron, copper, chromia and cobalt (U. S. Patent No. 4,705,903), a catalyst composed of a base treated hydrogenation catalyst from groups VIA or VIII of the Periodic Table (U. S. Patent No. 4,742,179), a catalyst consisting essentially of nickel, copper, chromium and barium (U. S. Patent No. 4,873,380), a catalyst composed of a metal phthalocyanine promoted with a rhenium compound (U. S. Patent No. 4,910,349), a catalyst composed of a base promoted metal phthalocyanine compound (U. S. Patent No. 4,912,269), a catalyst composed of a soluble ruthenium compound promoted with a bidentate ligand (U. S. Patent No. 4,912,033), a catalyst composed of a metal porphine such as iron (III) or manganese (III) promoted with an alkyl thiol or an amine, a catalyst composed of an imidazole promoted metal phthalocyanine compound (U. S. Patent No. 4,912,266), (U. S. Patent No. 4,922,034), a catalyst composed of a metal phthalocyanine promoted with a thiol and a free radical inhibitor (U. S. Patent No. 4,922,035), a catalyst composed of a borate promoted metal phthalocyanine (U. S. Patent No. 4,922,036), or a catalyst composed of a soluble ruthenium compound and an iron compound such as an acetate, a borate, a bromide, a chloride, a 1,3-propanedionate, a 2-ethyl-hexanoate, an iodide, a nitrate, a 2,4-pentanedionate, a perchlorate or a sulfate (U. S. Patent No. 5,025,113). As stated, when isobutane is reacted with molecular oxygen, the principal products of the reaction are tertiary butyl alcohol and tertiary butyl hydroperoxide. However, minor amounts of other contaminants are also formed. A minor amount of water will be formed, which will normally amount to 0.5 to 1 wt.% of the reactor effluent. The amount of byproduct water that is produced is a function of the severity of the reaction conditions employed and will tend to increase as the severity of the reaction conditions is increased. As indicated, tertiary butyl hydroperoxide is useful as a raw material for the manufacture of tertiary butyl alcohol. The tertiary butyl alcohol can be formed by catalytic decomposition of the tertiary butyl hydroperoxide. In the Williams et al. process disclosed in U. S. Patent No. 3,472,876, an oxygen-containing gas was charged to a reactor containing isobutane and an oxidation catalyst to provide a reaction mixture comprising tertiary butyl alcohol, tertiary butyl hydroperoxide, acetone, and tertiary butyl ether. The reported results in the patent indicate that there was a comparatively low rate of conversion and a comparatively poor selectivity of the reaction to tertiary butyl alcohol. In accordance with the present invention, a solvent solution of a tertiary butyl hydroperoxide charge stock is brought into contact with a catalytically effective amount of a hydroperoxide decomposition catalyst in a hydroperoxide decomposition reaction zone in liquid phase, preferably with agitation, to convert the tertiary butyl hydroperoxide to decomposition products, principally tertiary butyl alcohol, the hydroperoxide decomposition catalyst being a supported hydroperoxide decomposition catalyst consisting essentially of alumina having deposited thereon from 0.1 to 1 wt.% of a mixture of palladium and gold in the ratio of 0.01 to 1 part of gold per part of palladium, and tertiary butyl alcohol is recovered from the products of the hydroperoxide decomposition reaction. In accordance with a preferred embodiment of the present invention, the hydroperoxide decomposition catalyst is diluted with titania or zirconia. The tertiary butyl alcohol will not be the only decomposition product that is formed. Minor amounts of other oxygen-containing materials will also be formed. The tertiary butyl alcohol that is recovered from the decomposition reaction mixture will be contaminated with the oxygenated impurities. The starting materials for the process of the present invention are a tertiary butyl hydroperoxide feedstock and a supported palladium/gold catalyst. The Tertiary Butyl Hydroperoxide Feedstock The tertiary butyl hydroperoxide charge stock may comprise an isobutane oxidation product wherein the tertiary butyl hydroperoxide is dissolved in a mixture of isobutane and tertiary butyl alcohol or may comprise an isobutane oxidation product diluted by the addition of tertiary butyl alcohol, such that the solution of tertiary butyl alcohol in the mixture of isobutane with tertiary butyl alcohol contains from 5 to 30 wt.% of tertiary butyl hydroperoxide. A surprising and unexpected increase in the yield of tertiary butyl alcohol is obtained with a feedstock comprising tertiary butyl hydroperoxide dissolved in a solvent mixture of isobutane with tertiary butyl alcohol. The isobutane reaction product may be charged to a distillation zone where unreacted isobutane is removed as a distillate fraction for recycle to thereby provide a solution of tertiary butyl hydroperoxide in tertiary butyl alcohol containing 5 to 30 wt.% of tertiary butyl hydroperoxide. The Catalyst System The hydroperoxide decomposition catalyst to be used in accordance with the present invention consists essentially of alumina having deposited thereon from 0.1 to 1 wt.% of a mixture of palladium and gold in the ratio of 0.01 to 1 part of gold per part of palladium. In accordance with a preferred embodiment of the present invention, the hydroperoxide decomposition catalyst is diluted with from 100 to 500 wt.% of titania or zirconia, based on the weight of the alumina. Catalytic Decomposition of Tertiary Butyl Hydroperoxide The process of the present invention may be conducted batchwise in kettles or by continuously passing the reactants through a tubular reactor. The catalytic decomposition of the tertiary butyl hydroperoxide is preferably conducted at a temperature within the range of 20° to 250°C, preferably 60° to 120°C, and more preferably at a temperature of 80° to 100°C. The reaction is preferably conducted at a pressure sufficient to keep products and reactants in liquid phase, such as a pressure of 0.1 to 69 MPa (0 to 10,000 psig), preferably 0.1 to 7.0 MPa (0 to 1,000 psig) may be used, if desired. Flow rates of the charge solution to the reaction zone should be adjusted in order to provide an appropriate contact time within the reactor. In a batch process, the holding time may suitably be from 0.5 to 10 hours, and more preferably 1 to 3 hours. In accordance with the most preferred embodiment of the present invention, isobutane is reacted with oxygen in an oxidation zone under oxidation reaction conditions including a temperature of 135 to 155°C., a pressure of 2.1 to 5.6 MPa (300 to 800 psig), and a holding time of 2 to 6 hours to provide an initial oxidation reaction product comprising unreacted isobutane, tertiary butyl hydroperoxide, tertiary butyl alcohol, and oxygen-containing by-products. The initial oxidation reaction product is then used as the tertiary butyl hydroperoxide charge stock of the present invention. If the concentration of tertiary butyl hydroperoxide in the tertiary butyl hydroperoxide charge stock is more than 30 wt.% of the initial oxidation reaction product, the initial oxidation reaction product can be diluted with an amount of tertiary butyl alcohol sufficient to lower the concentration of the tertiary butyl hydroperoxide to a desired percentage, to provide, for example, a tertiary butyl hydroperoxide charge stock containing from 15 to 25 wt.% of tertiary butyl hydroperoxide. Alternatively, the initial oxidation reaction product may be fractionated in any appropriate manner (e.g., by distillation in a distillation zone) to remove the isobutane therefrom for recycle and to provide a solution of tertiary butyl hydroperoxide and tertiary butyl alcohol which will normally contain from 5 to 30 wt.% of tertiary butyl hydroperoxide. The solution of tertiary butyl hydroperoxide in tertiary butyl alcohol is then charged to a catalytic hydroperoxide decomposition zone where it is brought into contact with an alumina supported palladium/gold catalyst to substantially selectively convert the tertiary butyl hydroperoxide to tertiary butyl alcohol with high yields and selectivities. The process of the present invention may be practiced in a continuous manner by continuously charging the tertiary butyl hydroperoxide charge stock to a reactor containing a fixed bed of pelleted hydroperoxide decomposition catalyst, at a space velocity suitably in the range of 0.5 to 3 volumes of tertiary butyl hydroperoxide charge stock per volume of catalyst per hour. Preferably, the space velocity is within the range of 1 to 2 volumes of tertiary butyl hydroperoxide charge stock per volume of catalyst per hour. The reaction product from the tertiary butyl hydroperoxide decomposition step may then be fractionated in any suitable manner, such as by distillation to recover the tertiary butyl alcohol. EXAMPLES The invention will be further illustrated by the following non-limiting examples. The reactor was a stainless steel tube (13mm x 736mm) which was electrically heated. Liquid feed was pumped into the bottom of the reactor. Pressure regulation was with a Skinner Uni-Flow® valve and a Foxboro® controller. The liquid feed was pumped with a Ruska® dual drive pump. 20% TBHP was prepared from 55% isobutane peroxidation reactor effluent by diluting with commercial TBA. Analysis of the reactor effluent was by Gas Chromatography. Details are given in the following tables. Example 1 In this example, the catalyst consisted essentially of gold-promoted palladium supported on alumina. CATALYTIC CONVERSION OF TERT-BUTYLHYDROPEROXIDE TO TERT-BUTYLALCOHOL RUN A 1 2 3 4 Catalyst (.2% Pd, .08% Au on Al 2 O 3 ) Catalyst (cc) 100 100 100 100 Pressure (MPa) 2.1 2.1 2.1 2.1 Feed Rate (cc/Hr.) 50 50 50 50 Temperature (°C) 40 60 80 100 Time on Stream (Hr) 4 4 4 4 Space Vel. (cc/cc) 0.5 0.5 0.5 0.5 TBHP Conversion (mol.%) 56.3 82.7 92.9 99.6 IB Conversion (mol.%) 13.1 0.0 13.4 3.5 Sel. Acetone (mol.%) 0.2 2.3 6.9 6.8 Sel. Methanol (mol.%) 0.0 0.2 0.7 0.5 Sel. TBA (mol.%) 99.8 91.7 86.9 89.5 Sel. DTBP (mol.%) 0.0 6.1 6.1 3.7 Composition, wt% C3= 0.019 0.020 0.023 0.029 0.029 Isobutane 57.704 50.167 58.187 49.961 55.712 MEOH /MF 0.101 0.089 0.112 0.142 0.136 Acetone 1.128 1.139 1.346 1.875 1.915 TBA 21.338 38.448 34.791 43.904 40.044 DTBP 0.681 0.404 1.418 1.518 1.220 TBHP 18.084 7.894 3.126 1.291 0.079 CATALYTIC CONVERSION OF TERT-BUTYLHYDROPEROXIDE TO TERT-BUTYLALCOHOL RUN A 5 6 7 8 Catalyst (.2% Pd, .08% Au on Al 2 O 3 ) Catalyst (cc) 100 100 100 100 Pressure (MPa) 2.1 2.1 2.1 2.1 Feed Rate (cc/Hr.) 50 50 50 50 Temperature (°C) 40 60 80 100 Time on Stream (Hr) 4 4 4 4 Space Vel. (cc/cc) 0.5 0.5 0.5 0.5 TBHP Conversion (mol.%) 21.7 62.9 87.8 96.5 IB Conversion (mol.%) 1.2 n.d. 0.3 7.5 Sel. Acetone (mol.%) 2.5 1.9 4.7 7.6 Sel. Methanol (mol.%) 0.5 0.2 0.5 1.0 Sel. TBA (mol.%) 88.4 92.1 90.6 88.1 Sel. DTBP (mol.%) 9.1 6.0 4.7 4.3 Composition, wt% Isobutane 57.704 56.992 59.018 57.534 53.360 MEOH /MF 0.101 0.108 0.110 0.131 0.163 Acetone 1.128 1.191 1.265 1.605 1.988 TBA 21.338 25.640 30.712 36.183 41.556 DTBP 0.681 0.971 1.237 1.291 1.285 TBHP 18.084 14.165 6.709 2.198 0.631 CATALYTIC CONVERSION OF TERT-BUTYLHYDROPEROXIDE TO TERT-BUTYLALCOHOL RUN A 9 10 11 Catalyst (.2% Pd, .08% Au on Al 2 O 3 ) Catalyst (cc) 100 100 100 Pressure (MPa) 2.1 2.1 2.1 Feed Rate (cc/Hr.) 100 100 100 Temperature (°C) 60 80 100 Time on Stream (Hr) 4 4 4 Space Vel. (cc/cc) 1.0 1.0 1.0 TBHP Conversion (mol.%) 56.0 83.2 95.7 IB Conversion (mol.%) n.d. 11.0 12.9 Sel. Acetone (mol.%) 1.6 6.9 11.3 Sel. Methanol (mol.%) 0.1 4.7 6.1 Sel. TBA (mol.%) 93.0 88.0 85.2 Sel. DTBP (mol.%) 5.4 5.0 3.5 Composition, wt% Isobutane 57.704 60.017 51.337 50.249 MEOH /MF 0.101 0.106 0.351 0.477 Acetone 1.128 1.232 1.801 2.386 TBA 21.338 28.601 40.571 43.475 DTBP 0.681 1.121 1.292 1.172 TBHP 18.084 7.959 3.039 0.773 CATALYTIC CONVERSION OF TERT-BUTYLHYDROPEROXIDE TO TERT-BUTYLALCOHOL RUN A 12 13 14 Catalyst (.2% Pd, .08% Au on Al 2 O 3 ) Catalyst (cc) 100 100 100 Pressure (MPa) 2.1 2.1 2.1 Feed Rate (cc/Hr.) 200 200 200 Temperature (°C) 60 80 100 Time on Stream (Hr) 4 4 4 Space Vel. (cc/cc) 2.0 2.0 2.0 TBHP Conversion (mol.%) 22.6 67.9 92.4 IB Conversion (mol.%) 6.1 16.7 16.9 Sel. Acetone (mol.%) 5.2 9.1 15.7 Sel. Methanol (mol.%) 1.3 1.4 2.9 Sel. TBA (mol.%) 84.1 83.2 79.5 Sel. DTBP (mol.%) 10.7 7.7 4.8 Composition, wt% Isobutane 57.704 54.157 48.039 47.959 MEOH /MF 0.101 0.120 0.163 0.273 Acetone 1.128 1.264 1.849 2.821 TBA 21.338 28.374 41.215 44.881 DTBP 0.681 1.036 1.443 1.327 TBHP 18.084 13.996 5.799 1.383 It will be noted from Tables 1-4 that conversion of the tertiary butyl hydroperoxide was consistently in excess of 90% only at a temperature of 100°C. The selectivity to TBA is somewhat higher in the presence of IB. We believe that at least a portion of the IB is converted to TBA. The selectivity to TBA is consistently higher at lower temperatures and drops off at higher temperatures. The selectivity to DTBP is also higher at lower temperatures. The DTBP can be isolated for sale by a number of methods (see, for example, US-A-4,810,809) or it may be converted to additional TBA by any of the methods disclosed in the prior art. The selectivity to the lower value by-products acetone and methanol are higher at higher temperatures. One must choose between a conversion and selectivity which is most economical. Example 2 In Example 2, the catalyst was composed of 20 wt.% of the alumina-supported, gold promoted palladium catalyst of Example 1 diluted with 80 wt.% of titania. Note from Tables 5-7 that with only 20 wt.% of the catalyst of Example 1, the conversion of tertiary butyl hydroperoxide was about 90% of the conversion obtained in Example 1. This is especially significant since Pd and Au catalysts are quite expensive. The "dilution" of the Pd/Au catalyst with the more economical TiO 2 gave a catalyst which is almost as reactive as the Pd/Au catalyst alone. Conversion/selectivity remains high. CATALYTIC CONVERSION OF TERT-BUTYLHYDROPEROXIDE TO TERT-BUTYLALCOHOL RUN B 15 16 17 18 19 Catalyst 20 cc (.2% Pd, .08% Au on Al 2 O 3 ) 80 cc Titania Catalyst (cc) 100 100 100 100 100 Pressure (MPa) 2.1 2.1 2.1 2.1 2.1 Feed Rate (cc/H) 50 50 50 50 50 Temperature (°C) 60 70 80 90 100 Time on Stream (Hr) 4 4 4 4 4 Space Vel. (cc/cc) 0.5 0.5 0.5 0.5 0.5 TBHP Conversion (mol.%) 32.7 75.8 82.0 82.9 87.0 IB Conversion (mol.%) 26.0 5.0 3.8 4.4 15.8 Sel. Acetone (mol.%) 12.0 4.3 4.8 8.0 10.4 Sel. Methanol (mol.%) 2.2 0.7 1.1 1.1 1.8 Sel. TBA (mol%) 62.8 89.8 89.8 87.0 82.5 Sel. DTBP (mol.%) 25.2 5.8 5.4 5.1 7.1 Remarks H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis Composition, wt.% Isobutane 70.468 52.139 66.941 67.785 67.359 59.351 MEOH/MF 0.103 0.138 0.130 0.146 0.148 0.179 Acetone 0.930 1.285 1.226 1.283 1.525 1.742 TBA 13.739 35.002 26.889 26.811 27.018 34.924 DTBP 0.267 1.202 0.768 0.770 0.744 0.970 TBHP 13.980 9.402 3.388 2.522 2.388 1.814 CATALYTIC CONVERSION OF TERT-BUTYLHYDROPEROXIDE TO TERT-BUTYLALCOHOL RUN B 20 21 22 23 24 Catalyst 20 cc (.2% Pd, .08% Au on Al 2 O 3 ) 80 cc Titania Catalyst (cc) 100 100 100 100 100 Pressure (MPa) 2.1 2.1 2.1 2.1 2.1 Feed Rate (cc/H) 100 100 100 100 100 Temperature (°C) 60 70 80 90 100 Time on Stream (Hr) 4 4 4 4 4 Space Vel. (cc/cc) 1.0 1.0 1.0 1.0 1.0 TBHP Conversion (mol.%) 19.8 41.8 29.0 45.7 84.7 IB Conversion (mol.%) 1.4 2.5 3.7 6.1 11.6 Sel. Acetone (mol.%) 3.8 3.5 4.9 6.1 10.3 Sel. Methanol (mol.%) 1.0 0.7 1.5 1.5 2.2 Sel. TBA (mol.%) 89.5 90.6 89.2 88.5 85.4 Sel. DTBP (mol.%) 6.7 6.0 5.9 5.4 4.3 Remarks H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis Composition, wt.% Isobutane 70.468 69.484 68.722 67.844 66.195 62.267 MEOH/MF 0.103 0.113 0.118 0.124 0.136 0.195 Acetone 0.930 0.998 1.061 1.058 1.182 1.715 TBA 13.739 17.240 20.826 19.989 23.660 32.117 DTBP 0.267 0.418 0.549 0.461 0.545 0.684 TBHP 13.980 11.209 8.138 9.919 7.590 2.140 CATALYTIC CONVERSION OF TERT-BUTYLHYDROPEROXIDE TO TERT-BUTYLALCOHOL RUN B 25 26 27 28 Catalyst 20 cc (.2% Pd, .08% Au on Al 2 O 3 ) 80 cc Titania Catalyst (cc) 100 100 100 100 Pressure (MPa) 2.1 2.1 2.1 2.1 Feed Rate (cc/H) 200 200 200 200 Temperature (°C) 70 80 90 100 Time on Stream (Hr) 4 4 4 4 Space Vel. (cc/cc) 2.0 2.0 2.0 2.0 TBHP Conversion (mol.%) 15.4 42.1 76.3 81.8 IB Conversion (mol.%) 6.1 15.3 2.0 7.4 Sel. Acetone (mol.%) 8.2 9.6 5.4 9.1 Sel. Methanol (mol.%) 2.6 2.5 1.1 2.0 Sel. TBA (mol%) 80.9 81.2 90.7 87.2 Sel. DTBP (mol.%) 10.8 9.2 3.8 3.7 Remarks H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis Composition, wt.% Isobutane 70.468 66.195 59.662 69.050 65.266 MEOH/MF 0.103 0.123 0.155 0.146 0.185 Acetone 0.930 1.044 1.294 1.304 1.602 TBA 13.739 19.717 29.274 24.863 28.934 DTBP 0.267 0.455 0.706 0.600 0.611 TBHP 13.980 11.834 8.100 3.308 2.541 Example 3 In Example 3, the catalyst was composed of 20 wt.% of the alumina-supported, gold promoted palladium catalyst of Example 1 diluted with 80 wt.% of zirconia. Note from Tables 8 and 9 that with only 20 wt.% of the catalyst of Example 1, the conversion of tertiary butyl hydroperoxide was about 95% of the conversion obtained in Example 1. Again, the dilution of the more expensive Pd/Au catalyst with ZrO 2 gave a catalyst which was almost as active ad the Pd/Au catalyst alone. There was not a significant conversion/selectivity loss to desired products. CATALYTIC CONVERSION OF TERT-BUTYLHYDROPEROXIDE TO TERT-BUTYLALCOHOL RUN C 29 30 31 32 33 Catalyst 20 cc (.2% Pd, .08% Au on Al 2 O 3 ) 80 cc Zirconia Catalyst (cc) 100 100 100 100 100 Pressure (MPa) 2.1 2.1 2.1 2.1 2.1 Feed Rate (cc/H) 100 100 100 100 100 Temperature (°C) 60 70 80 90 100 Time on Stream (Hr) 4 4 4 4 4 Space Vel. (cc/cc) 1.0 1.0 1.0 1.0 1.0 TBHP Conversion (mol.%) 35.1 56.4 79.5 87.8 94.1 IB Conversion (mol.%) 3.8 4.3 4.9 5.1 7.1 Sel. Acetone (mol.%) 6.8 5.2 6.7 9.5 15.1 Sel. Methanol (mol.%) 1.5 0.9 0.9 1.2 2.0 Sel. TBA (mol.%) 85.9 88.3 88.3 86.2 81.2 Sel. DTBP (mol.%) 7.3 6.5 5.0 4.3 3.8 Remarks H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis Composition, wt.% Isobutane 71.310 68.580 68.244 67.822 67.639 66.243 MEOH/MF 0.151 0.177 0.176 0.186 0.202 0.240 Acetone 0.844 1.052 1.102 1.307 1.574 2.085 TBA 13.137 20.249 23.195 26.448 27.535 29.229 DTBP 0.259 0.542 0.663 0.699 0.673 0.649 TBHP 13.568 8.804 5.919 2.777 1.652 0.795 CATALYTIC CONVERSION OF TERT-BUTYLHYDROPEROXIDE TO TERT-BUTYLALCOHOL RUN C 34 35 36 37 Catalyst 20 cc (.2% Pd, .08% Au on Al 2 O 3 ) 80 cc Zirconia Catalyst (cc) 100 100 100 100 Pressure (psig) 300 300 300 300 Feed Rate (cc/H) 200 200 200 200 Temperature (°C) 70 80 90 100 Time on Stream (Hr) 4 4 4 4 Space Vel. (cc/cc) 2.0 2.0 2.0 2.0 TBHP Conversion (mol.%) 45.8 79.5 86.7 91.3 IB Conversion (mol.%) 2.7 5.0 7.5 7.4 Sel. Acetone (mol.%) 5.4 7.2 11.3 15.6 Sel. Methanol (mol.%) 1.2 1.1 1.9 2.5 Sel. TBA (mol%) 88.7 87.9 84.5 80.7 Sel. DTBP (mol.%) 5.9 4.9 4.2 3.6 Remarks H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis H 2 O Free Basis Composition, wt.% Isobutane 71.310 69.353 67.709 65.993 66.016 MEOH/MF 0.151 0.178 0.194 0.232 0.262 Acetone 0.844 1.061 1.346 1.703 2.093 TBA 13.137 20.848 26.535 28.882 29.020 DTBP 0.259 0.557 0.687 0.657 0.623 TBHP 13.568 7.359 2.781 1.811 1.182 Comparative Example In Table 10, the catalyst was composed of 0.08 wt.% of palladium supported on alumina. Note that there was a significantly lower selectivity of the tertiary butyl hydroperoxide to tertiary butyl alcohol. In Table 11, the tertiary butyl hydroperoxide charge stock was passed over pelleted titania. Note that there was a significantly lower selectivity of the tertiary butyl hydroperoxide to tertiary butyl alcohol. In Table 12, the tertiary butyl hydroperoxide charge stock was passed over pelleted zirconia. Again, note that there was a significantly lower selectivity of the tertiary butyl hydroperoxide to tertiary butyl alcohol. It is surprising that the "dilution" of our active catalyst such as the Pd/Au catalyst with a poor-fair catalyst such as the ZrO 2 or TiO 2 catalysts disclosed would lead to a catalyst mixture which is almost as active as the Pd/Au catalyst alone. This system has the added advantage that it is much more economical. CATALYTIC CONVERSION OF TBHP TO TBA (CONTINUOUS REACTOR) RUN Catalyst Temp. (°C) Space Vel. TBHP Cv(%) Sel. TBA Sel. Acet. Sel. MeOH Sel. DTBP 6879-31-1 Pd (.08%) on Al 2 O 3 80 0.5 88.9 82.8 9.7 1.9 7.5 6879-31-2 100 0.5 93.2 83.3 11.6 2.6 5.1 6879-31-3 120 0.5 96.2 81.6 13.9 3.3 4.4 6879-31-4 140 0.5 97.4 82.0 14.0 2.9 4.0 6879-32-1 Pd (.08%) on Al 2 O 3 80 1.0 78.0 83.0 9.6 1.6 7.4 6879-32-2 100 1.0 88.7 80.3 14.9 3.2 4.7 6879-32-3 120 1.0 93.6 78.1 18.4 4.7 3.5 6879-32-4 140 1.0 97.0 77.0 20.4 5.9 2.7 6879-33-1 Pd (.08%) on Al 2 O 3 80 2.0 45.0 82.9 7.5 1.2 9.6 6879-33-2 100 2.0 85.7 79.9 15.7 3.9 4.4 6879-33-3 120 2.0 94.5 74.8 22.5 6.9 2.7 6879-33-4 140 2.0 96.9 73.7 24.1 7.9 2.1 CATALYTIC CONVERSION OF TBHP TO TBA (CONTINUOUS REACTOR) RUN Catalyst Temp. (°C) Space Vel. TBHP Cv(%) Sel. TBA Sel. Acet. Sel. MeOH Sel. DTBP 6906-14-1 TiO 2 80 0.5 22.5 80.5 11.6 1.3 7.9 6906-14-2 100 0.5 72.0 79.3 16.4 3.3 4.3 6906-14-3 120 0.5 92.7 66.4 31.0 8.5 2.5 6906-14-4 140 0.5 98.5 66.1 32.8 8.9 1.1 6906-15-1 TiO 2 80 1.0 8.3 0.0 0.0 0.0 0.0 6906-15-2 100 1.0 35.8 82.2 13.0 2.6 4.8 6906-15-3 120 1.0 89.2 70.4 27.5 8.1 2.1 6906-15-4 140 1.0 99.5 59.3 40.6 10.5 0.2 6906-16-1 TiO 2 80 2.0 3.4 0.0 0.0 0.0 0.0 6906-16-2 100 2.0 16.4 80.7 14.1 2.3 5.2 6906-16-3 120 2.0 55.1 76.9 20.0 3.5 3.0 6906-16-4 140 2.0 89.0 62.8 36.2 11.7 1.0 CATALYTIC CONVERSION OF TBHP TO TBA (CONTINUOUS REACTOR) RUN Catalyst Temp. (°C) Space Vel. TBHP Cv(%) Sel. TBA Sel. Acet. Sel. MeOH Sel. DTBP 6906-17-1 ZrO 2 80 0.5 19.7 81.1 10.8 1.3 8.2 6906-17-2 100 0.5 77.5 79.2 15.8 3.8 5.0 6906-17-3 120 0.5 100.0 67.5 30.2 7.8 2.3 6906-17-4 140 0.5 100.0 66.4 32.5 7.3 1.1 6906-18-1 ZrO 2 80 1.0 7.1 0.0 0.0 0.0 0.0 6906-18-2 100 1.0 53.9 80.8 13.7 3.3 5.6 6906-18-3 120 1.0 95.9 70.9 26.8 6.8 2.3 6906-18-4 140 1.0 96.9 63.6 35.6 8.2 0.8 6906-19-1 ZrO 2 80 2.0 4.5 0.0 0.0 0.0 0.0 6906-19-2 100 2.0 28.9 80.4 13.4 3.1 6.2 6906-19-3 120 2.0 83.0 85.8 11.6 7.0 2.6 6906-19-4 140 2.0 94.9 65.3 34.0 8.6 0.7

Claims: A method for the decomposition of tertiary butyl hydroperoxide to tertiary butyl alcohol, wherein a solvent solution of a tertiary butyl hydroperoxide charge stock is brought into contact with a hydroperoxide decomposition catalyst, characterized in that said hydroperoxide decomposition catalyst comprises alumina having deposited thereon a mixture of palladium and gold in the ratio of 0.01 to 1 part of gold per part of palladium, and titania and/or zirconia as a diluent. A method as claimed in Claim 1, wherein the solvent comprises tertiary butyl alcohol or a mixture thereof with isobutane. A method as claimed in Claim 1 or Claim 2, wherein a solution of a tertiary butyl hydroperoxide charge stock in tertiary butyl alcohol that contains from 5 to 30 wt.% of tertiary butyl hydroperoxide is brought into contact with a catalytically effective amount of a hydroperoxide decomposition catalyst in a hydroperoxide decomposition reaction zone in liquid phase with agitation under hydroperoxide conversion conditions including a temperature within the range of 20° to 250°C. and a pressure of 0.1 to 7.0 MPa (0 to 1,000 psig) to convert said tertiary butyl hydroperoxide to decomposition products, principally tertiary butyl alcohol, characterized in that said hydroperoxide decomposition catalyst consists essentially of alumina having deposited thereon from 0.1 to 1 wt.% of a mixture of palladium and gold in the ratio of 0.01 to 1 part of gold per part of palladium, and a diluent consisting essentially of titania and/or zirconia. A method as claimed in any one of Claims 1 to 3, wherein the temperature is in the range of 60° to 120°C and the pressure is 0.1 MPa to 7.0 MPa. A method as claimed in any one of Claims 1 to 4, wherein the catalyst is diluted with from 100 to 500 wt.% of titania, based on the weight of the alumina. A method as claimed in any one of Claims 1 to 4, wherein the catalyst is diluted with from 100 to 500 wt.% of zirconia, based on the weight of the alumina.

Inventors: SANDERSON JOHN RONALD, SANDERSON, JOHN RONALD
Applicants: HUNTSMAN SPEC CHEM CORP, HUNTSMAN SPECIALTY CHEMICALS CORPORATION
Application year: 1994
Main classification: C07C29
IPC codes: C07C27, B01J21, C07C29, C07B61, C07C31, B01J23